[Updated to include Nik Weaver's correction / improvement from the comments.]
I think this follows from the spectral radius formula:
$$\left\| a \right\|^2 = \rho(a^*a) = \lim_{k \to \infty} \left\| (a^*a)^k \right\|^{1/k} \leq \left\| a^*a \right\| \leq \left\| a^* \right\| \left\| a \right\|$$
This gives $\left\| a \right\|^2 \leq \left\| a^* \right\| \left\| a \right\|$, implying $\left\| a \right\| \leq \left\| a^* \right\|$. Applying the same argument to $a^*$ we get $\left\| a \right\| = \left\| a^* \right\|$, so the inequality above becomes:
$$\left\| a \right\|^2 \leq \left\| a^* a \right\| \leq \left\| a \right\|^2$$
which yields the C* identity, as desired.
(The inequalities above follow from the Banach algebra axiom $\left\| ab \right\| \leq \left\| a \right\| \left\| b \right\|$.)